Cluster-Mediated Water Adsorption on Carbon Nanopores

The adsorption isotherms of water at 303 K and N2 at 77 K on various kinds of porous carbons were compared with each other. The saturated amounts of water adsorbed on carbons almost coincided with amounts of N2 adsorption in micropores. Although carbon aerogel samples have mesopores of the great pore volume, the saturated amount of adsorbed water was close to the micropore volume which is much small than the mesopore volume. These adsorption data on carbon aerogels indicated that the water molecules are not adsorbed in mesopores, but in micropores only. The adsorption isotherms of water on activated carbon having micropores of smaller than 0.7 nm in width had no clear adsorption hysteresis, while the water adsorption isotherms on micropores of greater than 0.7 nm had a remarkable adsorption hysteresis above P/P0 = 0.5. The disappearance of the clear hysteresis for smaller micropores suggested that the cluster of water molecules of about 0.7 nm in size gives rise to the water adsorption on the hydrophobic micropores; the formation and the structure of clusters of water molecules were associated with the adsorption mechanism. The cluster-mediated pore filling mechanism was proposed with a special relevance to the evidence on the formation of the ordered water molecular assembly in the carbon micropores by in situ X-ray diffraction.     

Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Preparation of highly porous carbon from fir wood by KOH etching and CO2 gasification for adsorption of dyes and phenols from water

Fir wood was first carbonized for 1.5 h at 450 degrees C, then soaked in a KOH solution KOH/char ratio of 1, and last activated for 1 h at 780 degrees C. During the last hour CO2 was poured in for further activation for 0, 15, 30, and 60 min, respectively. Carbonaceous adsorbents with controllable surface area and pore structure were chemically activated from carbonized fir wood (i.e., char) by KOH etching and CO2 gasification. The pore properties, including the BET surface area, pore volume, pore size distribution, and pore diameter, of these activated carbons were first characterized by the t-plot method based on N2 adsorption isotherms. Fir-wood carbon activated with CO2 gasification from 0 to 60 min exhibited a BET surface area ranging from 1371 to 2821 m2 g(-1), with a pore volume significantly increased from 0.81 to 1.73 m2 g(-1). Scanning electron microscopic (SEM) results showed that the surfaces of honeycombed holes in these carbons were significantly different from those of carbons without CO2 gasification. The adsorption of methylene blue, basic brown 1, acid blue 74, p-nitrophenol, p-chlorophenol, p-cresol, and phenol from water on all the carbons studied was examined to check their chemical characteristics. Adsorption kinetics was in agreement with the Elovich equation, and all equilibrium isotherms were in agreement with the Langmuir equation. These results were used to compare the Elovich parameter (1/b) and the adsorption quantity of the unit area (q(mon)/Sp) of activated carbons with different CO2 gasification durations. This work facilitated the preparation of activated carbon by effectively controlling pore structures and the adsorption performance of the activated carbon on adsorbates of different molecular forms.     

Preparation of activated carbon from sawdust by zinc chloride activation

A series of activated carbons were prepared from sawdust by zinc chloride activation in different operation conditions. The effects of operation parameters such as impregnation ratio, activation temperature and time on the adsorption properties of activated carbons were measured and analyzed in order to optimize these operation conditions. The experimental results show that under the experimental circumstances studied, both the yield and the adsorption for iodine and methylene blue of activated carbon can reach a relatively higher value in the chemical activation process with the impregnation ratio of 100% ZnCl₂/sawdust in the activation temperature of 500 °C carbonized for 60–90 minutes which are the optimum activation conditions in making wood activated carbon. The most important operation parameter in chemical activation with zinc chloride was found to be the impregnation ratio.     

On the mechanisms of phenol adsorption by carbons

The removal of phenol and related compounds from dilute aqueous solutions by activated carbons corresponds to the coating of the micropore walls and of the external surface by a monolayer. This process is described by an analog of the Dubinin—Radushkevich—Kaganer equation. On the other hand, as suggested by immersion calorimetry at 293 K, in the case of concentrated solutions, the mechanism corresponds to the volume filling of the micropores, as observed for the adsorption of phenol from the vapor phase. The equilibrium is described by the Dubinin—Astakhov equation. It follows that the removal of phenol from mixtures with water depends on the relative concentrations, and the limiting factor for adsorption is either the effective surface area of the carbon, or the micropore volume.     

Dubinin"s theory and its contribution to adsorption science

Dubinin"s theory for the volume filling of micropores (TVFM), originally developed for the adsorption of single vapours by microporous solids such as activated carbons and zeolites, has gradually been extended to other areas. They include immersion calorimetry, the adsorption of water vapour and of mixtures, as well as adsorption from aqueous solutions. Recent studies in the field of adsorption from aqueous solutions, by activated carbons, suggest that the principle of temperature invariance is fulfilled and in the case of phenolic compounds a modified DRK equation can be used to predict the adsorption equilibrium over a certain range of temperatures. Computer modelling of CO₂ adsorption by carbons at 273 K leads to micropore distributions, which are in good agreement with those derived from other techniques. It also appears that the model isotherms in single slit-shaped micropores can be fitted to the Hill-de Boer isotherm, in agreement with mathematical studies of the origin of the Dubinin—Astakhov equation.     

Prediction of Carbon Dioxide Adsorption via Deep Learning

Porous carbons with different textural properties exhibit great differences in CO₂ adsorption capacity. It is generally known that narrow micropores contribute to higher CO₂ adsorption capacity. However, it is still unclear what role each variable in the textural properties plays in CO₂ adsorption. Herein, a deep neural network is trained as a generative model to direct the relationship between CO₂ adsorption of porous carbons and corresponding textural properties. The trained neural network is further employed as an implicit model to estimate its ability to predict the CO₂ adsorption capacity of unknown porous carbons. Interestingly, the practical CO₂ adsorption amounts are in good agreement with predicted values using surface area, micropore and mesopore volumes as the input values simultaneously. This unprecedented deep learning neural network (DNN) approach, a type of machine learning algorithm, exhibits great potential to predict gas adsorption and guide the development of next‐generation carbons.     

Thermal properties of pitch-polymer compositions and derived activated carbons

The evaluation of the possibilities to use coal-tar pitch modified with waste poly(ethylene terephthalate) or phenol?Cformaldehyde resin for the preparation of activated carbons was carried out. The measurement of thermal analysis (DSC), softening point, coking value, content of components insoluble in toluene and quinoline of pitch-polymer compositions were carried out. Coal-tar pitch and pitch-polymer compositions were carbonized and activated with steam at 800?°C to 50?% burn-off. For the obtained activated carbons the determination of thermal analysis (DSC), BET surface area on the basis of volumetric low-temperature adsorption of nitrogen, mesopore, and micropore volume from benzene adsorption/desorption isotherms (gravimetric McBain-Bakr method) were carried out.     

多孔活性炭孔径分布的表征

总结了利用气体吸附法表征多孔活性炭中孔和微孔孔径分布的各种方法。BJH方法和MP模型忽略了微孔内势能叠加效应,仅适合描述中孔孔径分布;HK模型和以Dubinin填充理论为基础的各种方法,考虑了微观下势能叠加的效果,在一定程度上能很好地描述微孔孔径分布;最近围绕GAI(GeneralizedAdsorptionIsotherm)而展开的利用密度范函理论(DFT,densityfunctiontheory)和巨正则系综蒙特卡罗(GCMC,grandcanonicalensemblemontecarlo)模拟确定微孔孔径分布的方法较好地克服了Dubinin理论中存在的缺点,是较好的两种方法,但其有效性还需要更多的实验结果来证明。     

Role of Microporosity of Activated Carbons on Their Adsorption Abilities for Phenols and Dyes

The amounts of adsorption of two commercial dyes, phenol, and 4-chlorophenol from water on activated carbons were measured at 30°C. The carbons were prepared from cane (bagasse) piths and were activated by steam. The activation temperature and time were in the ranges of 750–840°C and 2 h, respectively. It was shown that the isotherm data of all four solutes could be well fitted by the Langmuir equation under the conditions studied. The adsorption capacities of the solutes were correlated with the microporosity properties of the activated carbons including micropore volume and external surface area. Finally, the adsorption characteristics of the present carbons was compared with those prepared from various agricultural wastes.     

Specific Features of the Adsorption and Nuclear Magnetic Relaxation of Water Molecules in Active Carbons. 1. Relation between the Spin-Spin Relaxation of Adsorbed Water Molecules and Structural Parameters of Microporous Active Carbons

Relation between the spin-spin nuclear magnetic relaxation time T ₂ of adsorbed water molecules and parameters of microporous structure of carbon adsorbents is disclosed. The pattern of dependences of T ₂ on the relative pressure and the number of water molecules per one primary adsorption site (PAS) is governed by the pore sizes and the number and nature of PASs. At a complete micropore filling, the T ₂ value depends on the volume density of PASs in active carbons. In the absence of PASs in the micropores, T ₂ is equal approximately to 21 ms. The larger the volume density of PASs, the smaller the number of water molecules per one PAS at the complete filling of micropores; i.e., the looser the packing of water molecules. The results of studying active carbons by the pulsed ¹H NMR method agree well with the data of the adsorption method.     

Development of nonuniform micropore structure of carbon adsorbents during activation: adsorption and small-angle X-ray scattering studies

The development of the micropore structure of activated carbons during activation was studied by small-angle X-ray scattering and adsorption methods. A new method for the processing of experimental data was used; this method makes it possible to obtain curves of the dimension distribution of micropores from the intensities of small-angle X-ray scattering and the adsorption isotherm. In the initial stage of activation, up to burnouts 0.3, the micropore structure is uniform, micropores with radius of gyration under 0.5–0.6 nm dominate. When activation is more prolonged ( = 0.3÷0.67), a bimodal system withR ₁ ^max 0.6 nm andR ₂ ^max 0.85÷1.0 nm forms, and the volume of large micropores (supermicropores) exceeds that of small ones considerably.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 231–235, February, 1994.     

Guest-host encapsulation of microporous zeolites in ordered mesoporous materials by molecular simulations

The present work provides the first study of ordered mesoporous materials SBA-15 coated with microporous zeolites ZSM-5 using molecular simulations. Several model structures with characteristics such as periodic arrangement of mesopores, randomly arranged micropores, surface hydroxyls and bulk deformations of SBA-15 were used. Cartesian coordinates of ZSM-5 unit lattice were obtained from the literature and the 100 face of H-ZSM-5 unit cell was then placed on the surface of SBA-15 and the entire structure was equilibrated to obtain final configuration. The resulting structure was characterized using simulated small angle and wide angle X-ray diffraction, Connolly surface area (to compare BET area), accessible pore volume for nitrogen molecules (to compare with t-plot volume of micro and mesopores) and methane adsorption at 303 K. The orientation of ZSM-5 on the SBA-15 had no effect on the surface area, pore volume or adsorption capacity. In order to find out if the addition of microporous ZSM-5 should increase the total methane adsorption capacity due to addition of micropores, we studied adsorption on bare and coated SBA-15. However, total adsorption capacity was found to decrease, while the number of methane molecules adsorbed per unit cell of the SBA-15 structure increased. An existing experimental method (J. Am. Chem. Soc., 2004, 126, 14324) of the synthesizing hybrid ZSM-5/SBA-15 structure was studied using accessible micropore volume (by t-plot). It was found that the procedure made all the micropores inaccessible. A modification of the method or use of other host materials is suggested to use the benefits of narrow micropore distribution in ZSM-5.     

The effect of small micropores on methane adsorption of coals from Northern China

In this study, the effect of coal micropores on the adsorption properties, especially the Langmuir pressure (P _L ), was investigated by testing 11 coal samples from Northern China. The adsorption of CO₂ at 273 K was utilized to analyze the pore size distribution. The results of these coals show that micropore volume and micropore surface area are the major factors affecting the Langmuir volume (V _L ) but have weaker effects on P _L . Micropore filling theory considers that some smaller micropores with an obvious overlapping adsorption force cause volume filling adsorption. These micropores firstly reach saturated adsorption, controlling the adsorption volume at the low-pressure stage and thus have a great effect on P _L . Four times the methane molecular diameter, 1.5 nm, was assumed as the critical pore size with obvious overlapping adsorption force. The relationship between P _L and the proportion of the pore volume below 1.5 nm to the micropore volume was investigated, and it was found that the higher the volume proportion of these small micropores was, the smaller the P _L was, though two data points deviated from this trend. The reason for the anomalous coal samples could be the deviation from the assumed critical pore size of 1.5 nm for volume filling and the effects of the various micropore surface properties, which await further study. The micropore surface increases with increasing coal rank, as does V _L . The proportion of pore volume below 1.5 nm increases with coal rank, and P _L reverses. However, these relationships are discrete.     

Preparation and characterization of activated carbon from bagasse fly ash

Activated carbons from bagasse fly ash (BFA) were prepared by one step chemical activation using ZnCl₂ as activating agent, or combination method of chemical with CO₂ physical activation (physicochemical activation). The development of porosity was studied in correlation with the method of activation, activation temperature, and also the chemical weight ratio. A typical sample by the combination method at 600 °C and weight ratio of ZnCl₂:BFA = 2 exhibited micropore volume of 0.528 cc/g, mesopore volume of 0.106 cc/g and surface area of 1200 m²/g. For determining the adsorption capacity of the carbon samples in solutions, phenol and methylene blue equilibrium adsorption experiments were conducted. The properties and adsorption capacity of the synthesized activated carbons has been compared to commercial activated carbon (Norit^® SX Plus).     

Low-temperature adsorption of hydrogen on nanoporous aluminophosphates: effect of pore size

Several nanoporous aluminophosphates (AlPOs) have been used to analyze the effect of pore diameter on the hydrogen adsorption characteristics. The heat of adsorption and adsorption capacity per unit micropore volume increase with decreasing pore size. AlPOs with smaller micropores favorably adsorb hydrogen at relatively low pressures. This work demonstrates that small pore size and large micropore volume are beneficial for high hydrogen uptake.